Dry stable feed composition



July 1, 1958 c. w. STEWART DRY STABLE FEED COMPOSITION Filed Feb. 6,1956 FIG. 1

K mm wm wm wwww 7 14 DAYS STORAGE 5oc 7% CHARLES w. STEWART UnitedStates Patent Office 2,841,495 Patented .Jully 1958 DRY STABLE FEEDCOMPOSITION Charles W. Stewart, Hinsdale, Ill., assignor to CornProducts Refining Company, New York, N. Y., a corporation of New JerseyApplication February 6, 1956, Serial No. 563,752

Claims. (Cl. 99--2) This invention relates to a dry composition ofmatter containing carotenoid pigments, particularly xanthophyll, whichis stable against oxidative deterioration.

Xanthophyll oil which is contained in small quantities in corn (maize)gluten is recovered therefrom as a byproduct in the recovery of zeinfrom the gluten. This oil, because of the xanthophyll therein, has beenfound to be useful in poultry feeding to provide pigmentation in theskin, body fat, legs, comb and beak of the poultry, and also in eggyolk. In view of the low xanthophyll content of some feed compositions,it has been proposed to increase their pigmenting power by addingthereto the aforementioned xanthophyll oil or alfalfa xanthophyll oil.However, this proposal has not been successful because of the rapiddeterioration of xanthophyll, probably brought about by oxidation.

Xanthophyll in its natural state, for example in gluten, is stableagainst oxidative deterioration but recovered xanthophyll deterioratesrapidly, e. g., in 2 or 3 days time, when exposed to air in a thin filmsuchas would be involved in a coating on feed materials. Accordingly,there is a need for a composition of matter containing xanthophyll whichhas a stability at least equal to that contained in plant materials,such as yellow 'corn or corn gluten, or preferably, a higher stability;

It is an object of the present invention to provide a new composition ofmatter containing carotenoid pigments which has a stability againstoxid'ative d'eteriora-,

tion of these pigments equal to or superiorto that of plant materialscontaining carotenoid pigments in their natural state. It is a furtherobject to provide such a composition of uniform potency which issuitable for Still anotherobject. is to provide such a composition indry form. which.

use in animal and poultry feeds.

can be handled and shipped readily and stored for long periods of timewithout loss of xanthophyll content. Other objects will appearhereinafter.

I have found that xanthophyll which has been recovered from plantsources can be stabilized against oxidative deterioration by absorbingthe xanthophyll, dissolved in a suitable solvent, such as vegetable oil,on deoiled vegetable oil bearing materials,-e. g., spent corn or grainsorghum germ meal, and suitably coating this product followed by dryingif necessary. The coating may consist of any of the following: steepliquor; and various mixtures of steep liquor and carbohydrates, such assteep liquor-molasses (corn sugar molasses or cane sugar molasses)mixture, steep liquor-dextrose greens mixture, steep liquor-corn sirupmixture, the amount of steep liquor in the mixture being at least aboutdry basis. Optionally, there may be used in combination with theaforementioned coating materials for further stabilization a reducingagent or an antioxidant or a combination of the two.

Inasmuch as xanthophyll is; usually recovered from plant sources, e. g.,corn (maize), alfalfa, in the form may be used in mixing the DPPD withthe xanthophyll' 'oil by the germ meal.

oil as the source of xanthophyll, but xanthophyll itself may be usedalso, particularly where it is desired to produce a product having ahigh potency of xanthophyll.

The deoiled vegetable oil material which is particularly useful as thecarrier in the present invention is that left after. corn or grainsorghum germ has been passed through machines to expel the oil or aftersolvent extraction of the germ to recover oil or after a combination ofthese two methods of recovering oil. Commercially deoiled soybeans(soybean fiakes), deoiled cottonseed (cottonseed meal), deoiled flax(linseed meal) and similar materials may be used also.

In carrying out the process of the invention, the xanthophyll in theform of xanthophylloil, for example, is mixed with the spent germ meal,for example, and warmed to l20140 F. toreduce the viscosity of the oiland to drive out air from the capillaries of the germ with resultantincrease of the rate of absorption of the When an antioxidant is used,it is preferable to incorporate it in the oil before addition to thegerm meal but it may be added during the mixing of the germ meal andoil. The germ meal and oil are mixed for a sufficient time to allowmaximum absorption of the oil, 5 to 25 minutes usually being sufficient.If xanthophyll itself is used, it may be dissolved in. methyl or ethylalcohol and added to the germ meal.

After the xanthophyll has been absorbed by the germ meal, the. germ mealis then mixed with heavy steep liquor or steep liquor-carbohydratemixture. Thereafter the product is dried to the proper moisture level.The product may also be pelletized before drying. It appears that thesteep liquor alone or in combination with the carbohydrate acts as aprotective coating for the germ meal onto which the oil has beenabsorbed.

If it is desired to use a reducing agent, salts, such as sodiumbisulfite or sodium metabisulfite or other salts ducing agentsapparently prevent the product from darkening in color.

The: final product may be dried in conventional manner until. themoisture content is about 1 to 10 percent. Higher moisture contentsresult in darkening of the prodnot on storage.

The ratio of'germ meal to xanthophyll may vary over a Wide rangedepending upon the potency of xanthophyll desired in the final product.The greatest amount of xanthophyll oil which the spent germ will absorbis about 60 percent. If the potency of the xanthophyll oil is too highfor the desired use, it may be diluted with acidulated soap stock orvegetable oil, such as corn oil or grain sorghum oil.

The amount of protective coating, i. e., steep liquor orsteep-liquor-carbohydrate mixture may vary widely but should be at leastabout 35 percent, dry basis, of the entire mixture in order to beeffective. From the standpoint of handling the final mixture, it isadvisable not to use more than about 60 percent of the protectivecoating although there is no upper limit as far as preventing oxidativedeterioration of the xanthophyll. is concerned.

If an antioxidant is used, the amount may vary according to its potencyand amount permissible in the final product. When the preferredantioxidant, N, N-diphenylparaphenylenediamine (sometimes referred tohereinafter as DPPD), is used concentrations of 0.05 to 0.3 percent ofthe final product gave satisfactory stability. Inasmuch as DPPD is veryslowly soluble even in hot oil, acetone oil. Other suitable antioxidantsinclude butylated hydroxyanisole, butylated hydroxytoluene, 6-ethoxy-1,2 dihydroxy 2,2,4 trimethylquinoline.

. If a reducing agent is used, the amount may vary from 4 EXAMPLE nStabilized xanthophyll product on spent grain sorghum germ about 0.05to. about 3.0 percent of the total dried mix. 5 Sorghum grain germexpellel' Cake containing about 1, By means of my invention, it ispossible to produce a Percent Of Oil Was ground to P through 20 mashprod ct having a uniform potency in respect of xanthoscreen. Forty-fivegrams of this material was mixed with P yll- This can be accomplishedsimply by using a uni- 18 g. of Xanthophyll oil which had beenstandardized to form amount of a previously standardized Xanthophyll1820 P- P- xanthophyll y dllutiqn with acidlllated p solution, such asXanthophyll oil. Further a p d t 10 stock. One-tenth gram of DPPDdissolved in acetone was which is highly nutritious and of excellentstability in re- 21180 added to thfi a p y Oil. Oil and germ spect ofXanthophyll and other carotenoids is produced. e m d for 3 mlnutes at120 F. in a mechanical A granular product which can be blended withother feedmIXer- Then 94 of gram sorghum heavy steepwater ing' materialsis readily obtained, (42.6%, D. S.) was added followed by 0.1 g. ofsodium The following examples which are typical and ill t bisulfite.Mixing was conti nued for 5 minutes and the tive only will furtherillustrate the invention. In the p u dried as descrlbed 1 xa pl 1- taility data tables all parts are on dry substance basis. e glven below.

EXAMPLE I Stability of xanthophyll at 50 C.

. 20 Stabilized xanthaphyll product on spent corn germ Percent RemainingThree hundred and sixty grams of spent corn germ 7days 14days 2ldaysflakes was warmed to 120 to 140 F. in a steam jacketed mixing bowl.Xanthophyll oil (extracted from corn glu- Initial Xanthophyll content,325 p. p. m 88 73 70 ten) was diluted with acidulated soap stock to givea standardized Xanthophyll oil containing 1820 p. p. m. Xanthophyll and706 p. p. m. carotene. An acetone solu- EAM1 )LE HI tion containing 1.0g. DPPD was added to 240 g. of the The pr e re scri 1n EXan1p1e I wasused with standardized Xanthophyll oil and the whole slowly poured thecarriers and coating materials listed in Table I except into the spentgerm with continuous stirring. Complete that the procedure used withsorghum grain germ was absorption of the oil by the germ flakes wasobtained i that described in Example II to show the effect of variousabout 3 minutes at 120 F. Three hundred and twenty coating materialsalone and in combination with reducing grams of corn sugar molasses(hydrol) (75% D. 8.), agents and antioxidants. Thirty parts of carrier,50 parts 720 g. heavy corn steep liquor (50% D. S.) and 1.0 g. ofcoating material and 20 parts of Xanthophyll oil were sodium bisulfitewere added successively to the mix with used. The results are shown 1nTable I.

TABLE I Stability, 60 O.Percent Xanthophyll Re- Oarrier, 30 PartsCoating Material, Amount Antioxidant No. maining, Days D. S. 60 Parts D.S. or Reducing Agent Runs Corn gluten In all 20 70 49 36 2 5.5 PPD 1 2.00.3% DPPD 1% 1 5.0 NaHSO 3 25 7.0 4 70 52 47 do 3 78 01 54 steepwater 1%N aHS O3 3 83 72 69 steepwater hydroL..- 1% N aHSOe 3 99 84 61steepwater 0.2% DPPD 1 94 91 84 Steepwater+hydrol 0%, EIIJSIBPD 0.3% 899 106 106 Twenty parts Xanthophyll 011 used in each case.

Stability of xanthophyll at C.

Percent Remaining 7days 14days 21days Initial Xanthophyll content, 364p. p. m

The data in Table I show that reducing agents or antioxidants are noteflective in stabilizing Xanthophyll oil adsorbed on spent corn germwhen no exterior coating is applied. The data also show that hydrolalone is ineffective as a protective coating, while steepwater as acoating material produces a product with Xanthophyll stabilitycomparable to that of gluten meal. The data also show that a coatingcomposed of steepwater and soluble carbohydrate is superior tosteepwater alone. The addition of a small quantity of reducing agent,such as NaHSO results in an increased stabilization of the Xanthophyll.The data further show that uncoated germ with adsorbed Xanthophyll oilcontaining 0.3 percent DPPD loses percent of the Xanthophyll in 7 daysat 50 C. while a similar productcoated with steepwater retains 84percent of its Xanthophyll after 21 days at 50 C. When the Xanthophylloil impregnated germ containing DPPD is coated with a mixture ofsteepwater and hydrol with added NaHSO the xanthophyll retention after'21' days at 50 C. is 106 percent. This figure is within the range ofaccuracy of present analytical methods and' is interpreted to meancomplete protection.

Data from Table I are also shown in graph form in Figure I.Identification of curves is as follows:

(1) Xanthophyll oil on spent corn germ meal with antioXidant-no coating.

(2) Xanthophyll oil on spent corn germ meal.

(3) Xanthophyll oil germ meal coated with hydrol.

(4) Xanthophyll oil germ meal coated with steepwater.

(5) Xanthophyll oil germ meal'coated with steepwaterhydrol mix plusreducing agent.

(6) Xanthophyll oil germ meal plus DPPD (antioxidant) coated withsteepwater. I

(7) Xanthophyll oil germ meal plus antioxidant coated withsteepwater-hydrol mix and added reducing agent.

EXAMPLE 1v Spent corn germ-xanthophyll oil mixtures were coated with amixture of steep liquor and each of the following:

corn sirup unmixed, dextrose greens and hydrol, inac-- cordance with themethod described in Example I. The effect of sodium bisulfite on themixtureswasalso investigated. The results are shown in Table II.

EXAMPLE V This example shows the effect of sodium bisulfite and DPPD onspent corn germ-xanthophyll oil mixture coated with heavy steepwater.The results are shown in Table III.

EXAMPLE VI This example shows the effect of DPPD on spent corngerm-xanthophyll oil mixtures coated with steepwater. The results areshown in Table IV.

EXAMPLE VII This example shows the effect of antioxidants and reducingagents on spent corn germxanthophyll oil mixtures with and without aprotective coating. The results are shown in Table V.

e parts carbohydrate (D. B.) mixed with 60 parts steepwater D. S., then45 part used to coat parts of X-oil-g'erm meal mixture (40 X-oil, 6Ogerm).

Product pelleted.

b. The bisulfite was mixed With the carbohydrate 18 hrs. beioremxingwith the steepwater. 9 Days storage at 50 0. in open petri dish.

TABLE III Percentage Xanthophyll Remaining-Days Initial Xantho- NoAdditives 1% NaI-ISOa 0.0125% DPPD 1% NaHSO3.

hyll 0.01257 DPPD one.

71 54 48 76 64 56 86 70 70 B6 80 76 71 52 44 71 52 5O 63 59 54 80 70 6274 50 48 65 75 71 89 B1 72 64 53 49 74 63 58 68 71 57 B8 72 63 X-oildiluted with acidulated soapstock to desired xanthophyll levels, 20parts; spent germ meal, 30 parts; steepwater 50% D. 5., 50 parts.Pelleted.

b Days at 50 O. in open petri dish.

TABLE IV Steep- DPPD Percentage Xanthophyll water, RemainingDays BaseMix Ratio, Percent Xanth. X-oilzgerm of Initial,

Product, Percent Percent p. p. m.

D. B. on X-oil on 7 e 14 21 Product 50 0. 75 0. 15 430 98 98 91 4o=eo 350.196 535 99 94 so 20 0. 24 620 88 90 69 50 1.0 0.2 486 94 91 84 40:6035 0. 26 565 84 81 20 0.32 680 89 72 66 50 1.0 0. 15 367 89 88 84 30:7035 0.195 470 88 76 20 0.24 548 80 70 72 Days at 50 0. in petri dish.

l 50% of product, D. B. Bas ed on calculated xanthophyll content.

2. A'composition according to claim 1 having incor-' porated therein anantioxidant.

3. A composition according to claim 1 having incorporated therein areducing agent.

4. A composition according to claim 1 having incorporated therein anantioxidant and a reducing agent.

5. A composition accordingto claim 1 wherein the carotenoid pigments aresupplied by xanthophyll oil, in amount not exceeding 60 percent of saidcarrier.

6. A process for producing a dry feed composition containing carotenoidpigments which comprises mixing a solution of carotenoid pigments and adeoiled vegetable oil bearing material and coating this mixture with acoating material from the group consisting of steep liquor and steepliquor in combination with any of the following: corn sirup,dextrosegreens, molasses, and mixtures thereof, the amount of steepliquor in said combination being at least about percent, dry basis; anddrying the resultant mixture; the amount of coating material being atleast 35 percent, dry basis, of the entire mixture.

7. Process according to claim 6 wherein an antioxidant is incorporatedin the mixture sometime prior to drying.

8. Process according to claim 6 wherein a reducing agent is incorporatedin the mixture sometime prior to drying.

9. Process according to claim 6 wherein a reducing agent and anantioxidant are incorporated in the mixture sometime prior to drying.

10. Process according to claim 6 wherein the solution of carotenoidpigments is xanthophyll oil, the amount not exceeding about percent ofsaid carrier.

References Cited in the file of this patent UNITED STATES PATENTS

1. A DRY FEED COMPOSITION CONTAINING CAROTENOID PIGMENTS WHICH IS STABLEAGAINT OXIDATIVE DETERIORATION COMPRISING A DEOILED VEGETABLE OILBEARING MATERIAL HAVING ABSORBED THERON CAROTENOID PIGMENTS AND COATEDWITH A COATING MATERIAL FROM THE GROUP CONSISTING OF STEEP LIQUOR ANDSTEEP LIQUOR IN COMBINATION WITH ANY OF THE FOLLOWING: CORN SLRUP,DEXTROSE GREENS, MOLASES, AND MIXTURES THEROF, THE AMOUNT OF STEEPLIQUOR IN SAID COMBINATION BEING AT LEAST ABOUT 50 PERCENT, DRY BASIS;THE AMOUNT OF COATING MATERIAL BEING AT LEAST 35 PERCENT, DRY BASIS, OFTHE ENTIRE MIXTURE.